ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 3, pp. 536–537. © Pleiades Publishing, Ltd., 2010. Original Russian Text © L.M. Abdrakhmanova, V.F. Mironov, L.A. Burnaeva, I.V. Konovalova, 2010, published in Zhurnal Obshchei Khimii, 2010, Vol. 80, No. 3, pp. 508–509.

LETTERS TO THE EDITOR

Cyclic P(III)-Phosphorylated Derivatives of Pamoic Acid. The Reaction of 4,4'-Methylene-bis(2-phenylnaphtho[2,3-d]1,3,2-dioxaphosphorin-4-one) with Chloral L. M. Abdrakhmanovaa, V. F. Mironova,b, L. A. Burnaevab, and I. V. Konovalovab a

Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center, Russian Academy of Sciences, ul. Arbuzova 8, Kazan, 420088 Tatarstan, Russia e-mail: [email protected] b

Ulyanov-Lenin Kazan State University, Kazan, Tatarstan, Russia Received October 5, 2009

DOI: 10.1134/S107036321003028X their biological properties [5–7]. In this paper we attempted to prepare the products of expansion of a six-membered ring to a seven-membered one by an example of reaction of chloral with a phosphorylated derivative of the pamoic acid containing phosphorus– carbon bond, 4,4'-methylene-bis(2-phenylnaphtho[2,3-d]1,3,2-dioxaphosphorin-4-one) (II). Direct phosphoylation of acid I with PCl3 did not give an unambiguous result [8], so we synthesized compound II in two steps: The silylation of acid I with hexamethyldisilazane followed by the reaction of the acid I O-trimethylsilyl derivative with dichlorophenylphosphine.

The mixed cyclic anhydride derivatives of natural hydroxycarbocylic acids, as well as of phosphorous or phosphonous acids are convenient reagents for the synthesis of heterocycles with predefined structure. Such acids react with activated unsaturated compounds under mild conditions, readily cleaving the macroergic RO–C(O) fragment and forming the products of cyclic and acyclic structures [1–3]. Recently, by an example of hexafluoroacetone we demonstrated the possibility to involve also more complex objects in such processes, the P(III)-cyclic derivatives derived from the natural substance, 4,4'-methylene-bis(3,2-hydroxynaphthoic) (pamoic) acid (I) [4], interesting due to

O

O 7

COOH OH OH

O O

(1) 2(Me3Si)2NH (2) 2PhPCl2

O

P

P

Ph

9

CCl3CHO

10

6a

10a

II

O

5a 5 11

17

Ph

O

COOH I

8

6

III

4

O

12

3 CCl3 * *P Ph 13 _16 O 1 2 O O O *P Ph * CCl3 O

O

diastereomers. However, one of them (δP 31.2 ppm) dominates. In a similar reaction of the cycle expansion of 2-phenylnaphtho[d]1,3,2-dioxaphosphepine at the action of chloral [9] the stereoselectivity is very high: of the two possible 2-phenyl-2,5-dioxo-3-(trichloromethyl)naphtho[2,3-e]1,4,2-dioxaphosphepine dia-

Compound II reacts with the prochiral chloral under mild conditions with the formation of six stereoisomeric bis(naphtho-1,4,2-dioxaphosphepines) (III) (δP 33.6, 32.5, 31.6, 31.2, 29.3, 28.7 ppm) in the ratio 4:5:5:33:4:9. This reaction gives rise to four chiral center resulting in the formation of a mixture of 536

CYCLIC P(III)-PHOSPHORYLATED DERIVATIVES OF PAMOIC ACID stereomers only one is formed. The difference in the solubility in methylene chloride of the diastereomers obtained provided a possibility to separate the dominating one. The remaining isomers were isolated as mixtures by reprecipitation of the reaction mixture from methylene chloride to pentane. Structure of individual diastereoisomers of compound III is proved by spectral methods. Compound II. a. To a solution of pamoic acid (8.25 g, 21.3 mmol) was added hexamethyldisilazane (18.0 g, 11.0 mmol). The reaction mixture was heated at 120°C for 30 h until the ammonia liberation ceased. The resulting orange precipitate of methylene-bis(2trimethylsiloxycarbonyl-3-trimethylsiloxynaphthalene) was filtered off, dried in a vacuum (0.1 mm Hg at 60°C), and used further without additional purification, yield 97%. b. A mixture of methylene-bis(2-trimethylsiloxycarbonyl-3-trimethylsiloxynaphthalene) (12.49 g, 20.1 mmol), CH2Cl2 (30 ml) and phenyldichlorophosphine (7.2 g, 40.2 mmol) was maintained at 20°C for 5 days, then the volatile compounds were removed by a vacuum distillation (12 mm Hg). The residue was dried in a vacuum (0.1 mm Hg, 60–70°C). Compound II was obtained as a dense vitreous substance of lightcream color, which was used further without additional purification. 31Р-{1H} NMR spectrum (CDCl3): δP 158.5 ppm (δ1), 157.7 ppm (δ2). Compound (III). A mixture of phosphonite II (2.28 g, 3.8 mmol), CH2Cl2 (10 ml), and chloral (1.51 g, 10.2 mmol) was maintained at 20°C for 4 days. During this period occurred a partial formation of compound III, which was filtered off, washed with diethyl ether, and dried in a vacuum (12 mm Hg). Yield 20%, mp 243-245°C. Found, %: C 51.97, H 2.49, Р 7.11. C39H24Cl6O8P2. Calculated, %: C 52.29, H 2.68, Р 6.93. IR spectrum, cm–1: 3435, 3057, 2894, 1742, 1623, 1594, 1504, 1448, 1440, 1369, 1344, 1285, 1257, 1206, 1160, 1143, 1122, 1077, 1056, 999, 932, 897, 875, 837, 821, 809, 783, 750, 690, 661, 644, 615, 536. The 1H NMR spectrum (DMF-d7, δ , ppm, J, Hz): 8.58 с (H6), 8.14 br.d (H7, 3JH8CCH7 8.4), 7.84–7.92 and 7.68, two m (H14–16), 7.79 br.d (H10, 3JH9CCH10 8.6), 7.64 m (H9), 7.56 m (H8), 6.80 d (H3, 2JРCH3 4.1), 3.66 m (H17). The 13C NMR spectrum (in parentheses is shown the multiplicity of the signal in 13C–{1H} NMR spectrum) (DMF-d7, δC, ppm, J, Hz): 79.98 d.d (d) (C3, 1 JHC3 151.1, 1JPC3 96.1), 165.08 d.d (s) (C5, 3JHC3ОC5

537

4.0–5.0, 3JHC6CC5 4.0–5.0), 121.04 br.s (s) (C5а), 135.32 d.d (s) (C6, 1JHC6 166.6, 3JHC7CC6 5.1), 131.35 m (s) (C6а), 130.62 br. d.d. d (br. s) (C7, 1JHC7 163.0, 3JHC9CC7 8.5, 3JHC6CC7 5.0–6.0), 130.62 d.d (s) (C8, 1JHC8 163.6, 3 JHC10CC8 8.1), 130.23 d.d (s) (C9, 1JHC9 163.6, 3JHC7CC9 7.3), 123.92 d.d (s) (C10, 1JHC10 161.8, 3JHC8CC10 7.3), 134.43 m (s) (C10а), 128.40 m (d) (C11, 3JРОCC11 4.8), 141.46 m (d) (C11а, 2JРОC11a 9.2), 94.40 d (d) (C12, 2 JРCC12 6.2), 127.92 d.m (d) (C13, 1JРC13 128.7, 3JHC15CC13 7.3), 131.86 d.d.d.d (d) (C14, 1JHC14 165.8, 2JРCC14 10.3, 3 JHC14'CC14 7.7, 3JHC16CC14 7.7), 129.40 d.d.d (d) (C15, 1 JHC15 165.1, 3JРCCC15 13.6, 3JHC15'CC15 7.7), 134.21 br.d.t (br.s) (C16, 1JHC16 164.5, 3JHC14CC16 7.7), 22.66 t (s) (C17, 1 JHC17 130.7). The 31Р–{1H} NMR spectrum (DMSOd6): δР 31.2 ppm (s). The NMR spectra were recorded on a Bruker Avance-400 instrument (1H, 400 MHz, 13C, 100.6 MHz, 31 P, 162.0 MHz). The IR spectrum was recorded on a Bruker Vector-22 instrument from a suspension of the substance in mineral oil. REFERENCES 1. Mironov, V.F., Gubaidullin, A.T., Konovalova, I.V., Ivkov, G.A, Litvinov, I.A., Burnaeva, L.M., Zyablikova, T.A., Romanov, S.V., and Mavleev, R.A., Zh. Obsch. Khim., 2000, vol. 70, no. 11, p. 1812. 2. Burnaeva, L.M., Mironov, V.F., Romanov, S.V., Ivkova, G.A., Shulaeva, I.L., and Konovalova, I.V., Zh. Obsch. Khim., 2001, vol. 71, no. 3, p. 525. 3. Mironov, V.F., Zagidullina, E.R., Ivkova, G.A., Dobrynin, A.B., Gubaidullin, A.T., Latypov, Sh.K., Musin, R.Z., Litvinov, I.A., Balandina, A.A., and Konovalova, I.V., Arkivoc, 2004, part 12, p. 95. 4. Burnaeva, L.M., Mironov, V.F., Abdrakhmanova, L.M., Ivkova, G.A., Balandina, A.A., Latypov, Sh.K., Konovalova, I.V., and Pudovik, A.N., Zh. Obsch. Khim., 2006, vol. 76, no. 8, p. 1394. 5. Reetz, M., Merk, C., and Mehler, G., Chem. Comm., 1998, no. 19, p. 2075. 6. Hu, H.-Y., Horton, J.K., Gryk, M.R., Prasad, R., Naron, J.M., Sun, D.-A., Hecht, S.M., Wilson, S.H., and Mullen, G.P., J. Biol. Chem., 2004, vol. 279, no. 38, p. 39736. 7. Fei, Z., Slavin, A., and Woollins, D., Polyhedron, 2001, vol. 20, no. 28, p. 3355. 8. Fonge, H., Chitneni, S.K., Lixin, J., Vunckx, K., Prinsen, K., Nuyts, J., Mortelmans, L., Bormans, G., Ni, Y., and Verbruggen, A., Bioconjugate Chem., 2007, vol. 18, no. 6, p. 1924. 9. Burnaeva, L.M., Mironov, V.F., Abdrakhmanova, L.M., Gubaidullin, A.T., Musin, R.Z., Ivkova, G.A., Litvinov, I.A., Latypov, Sh.K., Balandina, A.A., and Konovalova, I.V., Zh. Obsch. Khim., 2007, vol. 77, no. 4, p. 578.

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 3 2010